1.3-diaza-anthraquinones



Patented Oct. 17, 1939 2,176,413

Ls-mAzA-ANrnliadnmolsins Fritz Baumann and Heinz -Weri1e'r schweehten. Leverkusen-I. G. Werk, Germany, assignors-io' General Aniline Works, Inc.,' New *York,rN. Y., a corporation of Delaware No Drawing. Application jA pril [7, Serial No. 200,680. In Germany April-I6,'-1937 9 Claims. (Chadd-251') The present invention relates to new valuable E aia'rnpl 1 compounds. In accordance with our invention A Suspension of 10 parts of new products are obtained having p f phenyl-6.7-benzo-quinaioline in 200 parts of gw i a of afnphraquinone y SubJectmg aceticacidis heated to -95-.100 C., whereupon 5 .sq'ibenzo'qumazohne(to the actwn of q 11 mmo fchr cl acid,-which are dissolved in 5 oxidizing agents as are capable of converting 60 parts of {we acid: andglz parts' of water, anthracene into anthraquinone. The reaction f 'y -d T immediately proceeds as follows: ring loxidation issoon-finished. From. the green H solution thus formed thereare separated egg 0 yolk crystals which are filtered with suction at 10 N N \O-R room temperature, rinsed with acetic acid and l water and then dried. The oxidation product b ,-0x1dation process thus obtained represents the 1.3-diaza-2-hydroxy-4-phenylanthraquinone of the following R O R constitution:

It is to be understood'that R stands for the 3 'hydroxyl group, or aryl or for a; radical of a compound whichis capa'ble of being vatted. The (IP03 resulting product is a 1.3-diaza-anthraquinone. N 20 We-wish to-point out that every oxidizing agent which\ is capable of oxidizing. anthracene 1 into anthraquinonecan beemployed for our p ese t t o c q ac in an acid It can berecrystamze from nitrobenzene and di in pa cu ar in t e p esence ofelaciel has, almelti'ng point of 344 0.; it is soluble in 25 aeetpiceor su furic d, being p efer ed. sulfuric acid with a; yellow coloration and yields In the:fifl benzo-quinazolines used as starting bl g ae materialsthe benzene nucleus linked to the car- The;tgjhydlfoxyeaphenypgglbenzoquinazoline atoms 6 and 7 may be subtitllted Once can, for" instance, be obtained by heating Z-amiv several times by a halogen. Valuable products no 3 benzpy1 naphtha1eneI with urethane the 30 i are obtained by usingas starting materials 6.7- r e f' gl m a benzo-qui na'zoline's'beingsubstituted in 2- and 4positi on'. one of' them containing ahydroxyl a e 2 group and the other containingancaryliona 5 parts of 2A dihydroxy 6Lbenzmluinazoline t fgid gf u g 9 are suspended in the 20-fold quantity of acetic 35 a ifl x i y 0 I a an raqumone acid and oxidized at 100 C. with a solution of 8 our new vanapl-e'pmdp-cts generally-Speak" parts of chromic acid in acetic acid On cooling ing, valuable intermediates for the production of the 1 3 diam 2 4 dihydroxy ailthmquinone dyestufis for p vat dyestugs acld formedis su'ckedlofi, rinsed? with acetic acid and 40 wookdyespufisfor plgment dyestuffs ey can thenwithihot water. ;On-..drying the compound 40 be subjected to further reactions such as a halogenation or a sulfonation. Hydroxyl groups which may be present in 2- or l-position can be exchanged by a halogen, for instance, by recrystallizes from pyridine in splendid yellow needles; the free compound can also be recrystallized from about 100 parts of nitrobenzene. The dyestuff thus obtained is soluble in sulfuric acid acting thereupon with phosphorus-pentachloride. 45 In the halides thus obtained the halogen atom 2 22 igz g zigg the aqueous is capable of being easily exchanged. Therefore these halides can be subjected to further gfis' the followmg figures have been transformation, for instance, with amines which contain at least 1 hydrogen attached to the ni- 5 trogen. Preferably amines of anthraquinone or C E N other compounds which are capable of being vatted are employed. The following examples Found illustrate the invention without, however, re- Calculated stricting it thereto the parts being by weight. 55

Per cent Per cent Per cent The 1.3-dihydroxy-6.7-benzo-quinazoline is obtainable by causing 2-naphthylamino-3-carboxylic acid to react with urea.

Example 3 To a suspension: of lO-partspf 2-pheny-l-4ehydroxy-6fl benzo-quinazoline in 280'partsof 50 per cent sulfuric acid an excess of chromic acid is added while stirring at a temperature of 80 C ,;1 :j:

whereupon the 2-phenyl-4-hydroxy-6.TZebenzo quinazoline is dissolved while oxidizing; When the oxidation is finished thereactionproductis stirred into water, the precipitated crude -2- phenyl 4 hydroxy-1.3-diaza-anthraquinone is filtered off and purified by way of the sodium salt which is difficultly soluble in -diluted soda lye,

eventually adding sodium hypogchlorit'e, ;The

compound thus obtained can be recrystallized from nitrobenzene; it yields an orange vatand" is also soluble in sulfuiic acid with an orange .9 V Example 4 To a suspension of 2- (1'-'nitro-2 *arithraquinonyl) -4-hydroxy 6.7 benzo-quinazoline in 40 times the quantity of acetic acid there is gradually added whileiboiling excess chromic acid. When the reaction'is almost complete a product of the following constitution precipitates:

, which is filtered with suction and rinsed. n

crystallizing from nitrobenzene (it forms weak yellowish needles; it yields a brown vat from which on shaking violet flakes separate.

The 2 -(1' nitro-2f-anthraquinonyl) 4 hy-. dreary-6.7-benzo-quinazoline serving as starting materialhas been obtained .by causing 2naph-.

thalylamino-3-carbonamide to react with -.1- nitro-anthraquinone-2-carboxylic acid chloride in a pyridine caustic potash lye with ring closure. We claim: I v, 1. The compounds of the general.forinula 1 wherein oneofthe' R's-stands for the hydroxyl group and the other R stands for-a radical selected from the group consisting of hydroxyl, phenyl and a vattable p-quinoidic radical containing at least 3 condensed rings.

2. The compounds of the following formula wherein one of the Rs stands for the hydroxyl group and the other R stands for an anthraquinone.

6. The process which comprisessubjecting a 6.7-benzo-quinazoline to the action of such oxidizing agents as are capable of converting anthracene into anthraquinone.

7. The process which comprises subjecting a 6.7-benzo-quinazoline to the action of such oxidi zing agents as are capable of converting anthracene into anthraquinone in the presenceo an organic solvent. p

"8. The process which comprises subjecting a fifl -benzo-quinazoline to the action of such oxidizing agents as are capableof converting anthracene into anthra'quinone in the: presence of sulfuric acid, 7 p

QJIYhe'prQcess which comprises subjecting a 6.7 -benzo quinazoline to the action of an excessof chromic acid in thepresence of sulfuric acid;

FRITZ BAUMANN, HEINZ WERNER SCHWECHTEN. 

